CN102952399B - Environment-friendly flame retardant glass fiber reinforced polyamide 66 (PA66) material with high comparative tracking index (CTI) value and high glow wire ignition temperature (GWIT) value and preparation method thereof - Google Patents
Environment-friendly flame retardant glass fiber reinforced polyamide 66 (PA66) material with high comparative tracking index (CTI) value and high glow wire ignition temperature (GWIT) value and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an environment-friendly flame retardant glass fiber reinforced polyamide 66 (PA66) material with high comparative tracking index (CTI) value and high glow wire ignition temperature (GWIT) value, which comprises the raw material components by weight percent: 45-68% of PA66, 6-20% of compound fire retardant, 3-15% of antimonous oxide, 20-30% of glass fiber, 2-10% of compatilizer, 0.1-1% of antioxidant and 0.1-1% of oxide, wherein the compound fire retardant comprises brominated polystyrene, magnesium hypophosphite and talcum powder. The invention also discloses a preparation method of the environment-friendly flame retardant glass fiber reinforced PA66 material with high CTI value and high GWIT value. The composite material is higher in GWIT value and CTI value, better in flame retardant effect, environment-friendly in material and balanced in combination properties, thus being widely applied to products in the field of electronic electric appliances such as a low-voltage electronic capacitor shell, a load break switch, a carbon brush bracket, a moulded case circuit breaker and the like.
Description
Technical field
The present invention relates to technical field of composite materials, specifically, is a kind of high CTI value, high GWIT value environment-protection flame-proof fiberglass reinforced plastic PA66 material and preparation method thereof.
Background technology
Nylon (Nylon), Chinese name polymeric amide, English name Polyamide(is called for short PA), be on molecular backbone chain, contain recurring amide radical group-[NHCO]-thermoplastic resin general name.Its name is determined by the concrete carbonatoms of synthon, as: polycaprolactam (nylon 6, be called for short PA6), polyhexamethylene adipamide (nylon 66, be called for short PA66), poly-sebacic acid decamethylene diamine (nylon 1010, be called for short PA1010), polyhexamethylene sebacamide (NYLON610, be called for short PA610), nylon 11 (nylon 11 is called for short PA11), poly-lauramide (nylon 12, be called for short PA12), nylon 46 (nylon 46, be called for short PA46).PA degree of crystallinity is high, and fusing point is obvious; Surface hardness is large, abrasion performance, and frictional coefficient is little; There are self lubricity and noise reduction; Low-temperature performance is good, has certain thermotolerance (can use below 100 degree); Nontoxic, odorless, not mildew and rot, have self-extinguishing, good weatherability, but dyeability is poor.
21 century electronics, electric, communication, household electrical appliances, electromechanical equipment are to high-performance microization development, and more and more higher to the requirement of flame-retardant PA 66 material, meanwhile, along with the understanding of the mankind to environmental protection, Green Product is subject to common concern.Therefore, flame-retardant PA 66 Materials direction is: performance function flame-retardant PA 66 material becomes main flow; The kind of environmental type flame-retardant PA 66 material and demand are more and more; The production of flame-retardant PA 66 material is to many variety series future development; The use of fire retardant is to diversification, compound development.Traditional bromide fire retardant can not meet the requirement of high standard product, the fire retardant compound system that some are traditional, for example glass fibre+TDE+antimonous oxide compound system, glass fibre+brominated Polystyrene+antimonous oxide compound system, CTI value (the comparative tracking index of these compound systems, relative discharge tracking index) and GWIT value (glow-wire ignition temperature, glow-wire ignition temperature) not high, be not suitable for the power utilization environment of high request.
Chinese patent literature application number 200610028821.1, open day on January 16th, 2008, a kind of flame-proof enhancement PA 66 composition is disclosed, this flame-proof enhancement PA 66 composition is by PA66 base resin, glass, main flame retardant (more than 10000 brominated epoxy resin of molecular weight), auxiliary flame retardant antimonous oxide, toughening agent maleic anhydride grafting POE, stablizer hydrotalcite, lubricant stearic acid and oxidation inhibitor Hinered phenols and phosphorous acid esters composition, the PA66 composition satisfactory mechanical property of preparation, flame retardant effect is better, but the total content of main flame retardant and auxiliary flame retardant is higher, GWIT and the CTI situation of composition are not provided.Chinese patent literature application number 201110301621.X, open day on March 21st, 2012, announce a kind of halogen-free flame retarding strengthened PA 66 material and preparation method thereof, its composition of described PA66 material is by weight ratio: PA66 resin 34～41%, alkali-free long glass fibres 30～40%, the high red phosphorus master batch 15～18% of filling, CTI improving agent 1～3%, anticorrosion erosion resistant agent 3～5%, compatible toughening agents 3～5%, oxidation inhibitor 0.4～1%, lubricant 0.4～1%, owing to adopting red phosphorus master batch as fire retardant, increase substantially the CTI value of PA66 and reduced it to corrosion of metal, CTI value is up to 480V.But have not been reported about the compound PA66 material that integrates the advantages such as high GWIT value, high CTI value, environmental protection, over-all properties equilibrium.
Summary of the invention
The object of the invention is for deficiency of the prior art, a kind of high CTI value, high GWIT value environment-protection flame-proof fiberglass reinforced plastic PA66 material are provided.This matrix material glow wire temperature is higher, environmental protection, and over-all properties equilibrium, is applicable to Low-voltage Electronic capacitor case, load break switch, carbon brush supports, the electronic applications such as breaker of plastic casing.
One object more of the present invention is that the preparation method of a kind of high CTI value, high GWIT value environment-protection flame-proof fiberglass reinforced plastic PA66 material is provided.
For achieving the above object, the technical scheme that the present invention takes is:
A kind of high CTI value, high GWIT value environment-protection flame-proof fiberglass reinforced plastic PA66 material, described material comprises the feed composition of following weight percent content:
PA66 45%～68%，
Compound flame redundant 6%～20%,
Antimonous oxide 3%～15%,
Glass fibre 20%～30%,
Compatilizer 2%～10%,
Oxidation inhibitor 0.1%～1%,
Oxide compound 0.1%～1%,
Described compound flame redundant is made up of brominated Polystyrene, magnesium hypophosphite and talcum powder.
Described PA66 is polyhexamethylene adipamide, and its limiting viscosity is 2.8 dl/g.
Described compound flame redundant is made up of the feed composition of following weight percent content: brominated Polystyrene 50%, magnesium hypophosphite 25%, talcum powder 25%.
Described glass fibre is the alkali free glass fibre of surface through silane coupling agent processing.
Described compatilizer is maleic anhydride graft POE.
Described oxidation inhibitor is Hinered phenols antioxidant.
Described oxidation inhibitor is oxidation inhibitor 1330.
Described oxide compound is ferric oxide.
For realizing above-mentioned second object, the technical scheme that the present invention takes is:
A preparation method for high CTI value, high GWIT value environment-protection flame-proof fiberglass reinforced plastic PA66 material, comprises the steps:
(1) take each raw material according to above-mentioned weight percent;
(2) the various raw materials that weigh up are put into high mixer, mix 2～5 minutes, discharging, then uses twin screw extruder extruding pelletization.
The processing temperature of described twin screw extruder is 220～255 DEG C, and screw rod revolution is 30～40Hz.
The invention has the advantages that:
1, the present invention adopts BACN compound system, compares with traditional flame-retardant system, and in the situation that fire retardant percentage composition is identical, novel built system can make the GWIT value of material improve 50 DEG C to 100 DEG C, can pass through 850 DEG C of glowing filaments;
2, can make the GWIT value of material obviously improve adding of glass fibre, compatilizer can improve the impact property of material, improves materials processing mobility, reduces frictional coefficient, improves slipping;
3, Hinered phenols antioxidant can improve the ageing resistance of matrix material in antioxidant property and the use procedure of the course of processing, adopts oxide compound as the auxiliary agent of carrying high CTI value;
4, the present invention is under specific processing conditions, and raw material is better dispersed, and the residence time is short, adopts and shears slightly weak combination, prevents that fire retardant from decomposing, thereby has ensured the steady quality of material; GWIT value and the CTI value of the matrix material preparing are higher, flame retardant effect is better, matrix material environmental protection, over-all properties equilibrium, can be widely used in the product of the field of electronics such as Low-voltage Electronic capacitor case, load break switch, carbon brush supports, breaker of plastic casing.
Embodiment
Below embodiment provided by the invention is elaborated.
High CTI value of the present invention, high GWIT value environment-protection flame-proof fiberglass reinforced plastic PA66 material, described PA66 is commercially available polyhexamethylene adipamide, its limiting viscosity is preferably 2.8 dl/g, can be also other value of 2.0～3.2 dl/g scopes; Described compound flame redundant is made up of brominated Polystyrene (being called for short BPS), magnesium hypophosphite and talcum powder, and weight percent content is preferably BPS 50%, magnesium hypophosphite 25%, talcum powder 25%, and this fire retardant can effectively improve the GWIT value of matrix material; Described glass fibre is preferably the alkali free glass fibre of surface through silane coupling agent processing, and glass fibre is added in silane coupling agent, makes its surface through silane coupling agent processing, and it can make the GWIT value of material obviously improve; Described compatilizer can improve the impact property of material, can be maleic anhydride grafted polystyrene, imide-modified vinylformic acid, maleic anhydride graft PPO etc., is preferably maleic anhydride graft POE; Described oxidation inhibitor is preferably the oxidation inhibitor 1330 in Hinered phenols antioxidant, can also be antioxidant 1010, antioxidant 300, thio-2 acid dibasic acid esters etc., all can block, suppress or delay polymkeric substance oxidation or autoxidation process, can improve the ageing resistance in antioxidant property and the use procedure of matrix material in the course of processing; Described oxide compound is as the auxiliary agent of carrying high CTI value, can be aluminum oxide, magnesium oxide etc., is preferably ferric oxide.
In the preparation process of PA66 matrix material of the present invention, the various raw materials that weigh up are put into high mixer, mix 2～5 minutes, discharging, then uses twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 220～255 DEG C, and forcing machine comprises nine warm areas, wherein one section 220 DEG C, and two sections 250 DEG C, three sections 255 DEG C, four sections 255 DEG C, five sections 255 DEG C, six sections 240 DEG C, seven sections 230 DEG C, eight sections 230 DEG C, nine sections 230 DEG C, screw rod revolution is 30～40Hz.
the preparation (one) of embodiment 1 PA66 matrix material
The limiting viscosity of PA66 is 2.8 dl/g, the raw material that compound flame redundant is BPS 50%, magnesium hypophosphite 25% and talcum powder 25% by weight percent content forms, glass fibre is the alkali free glass fibre of surface through silane coupling agent processing, compatilizer is maleic anhydride graft POE, oxidation inhibitor is oxidation inhibitor 1330, and oxide compound is ferric oxide.
Take each feed composition: PA66 45% by following weight percent content, compound flame redundant 20%, antimonous oxide 4%, glass fibre 20%, compatilizer 10%, oxidation inhibitor 0.1%, oxide compound 0.9%.The each raw material weighing up is put into high mixer, mix 2 minutes, discharging, then uses twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 220～255 DEG C, and forcing machine comprises nine warm areas, wherein one section 220 DEG C, and two sections 250 DEG C, three sections 255 DEG C, four sections 255 DEG C, five sections 255 DEG C, six sections 240 DEG C, seven sections 230 DEG C, eight sections 230 DEG C, nine sections 230 DEG C, screw rod revolution is 30Hz.
the preparation (two) of embodiment 2 PA66 matrix materials
The limiting viscosity of PA66 is 2.8 dl/g, the raw material that compound flame redundant is BPS 50%, magnesium hypophosphite 25% and talcum powder 25% by weight percent content forms, glass fibre is the alkali free glass fibre of surface through silane coupling agent processing, compatilizer is maleic anhydride graft POE, oxidation inhibitor is antioxidant 1010, and oxide compound is ferric oxide.
Take each feed composition: PA66 55% by following weight percent content, compound flame redundant 8%, antimonous oxide 3%, glass fibre 30%, compatilizer 2%, oxidation inhibitor 1%, oxide compound 1%.The each raw material weighing up is put into high mixer, mix 5 minutes, discharging, then uses twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 220～255 DEG C, and forcing machine comprises nine warm areas, wherein one section 220 DEG C, and two sections 250 DEG C, three sections 255 DEG C, four sections 255 DEG C, five sections 255 DEG C, six sections 240 DEG C, seven sections 230 DEG C, eight sections 230 DEG C, nine sections 230 DEG C, screw rod revolution is 35Hz.
the preparation (three) of embodiment 3 PA66 matrix materials
The limiting viscosity of PA66 is 2.0 dl/g, and the raw material that compound flame redundant is BPS 45%, magnesium hypophosphite 30% and talcum powder 25% by weight percent content forms, and compatilizer is maleic anhydride graft PPO, and oxidation inhibitor is oxidation inhibitor 1330, and oxide compound is aluminum oxide.
Take each feed composition: PA66 50% by following weight percent content, compound flame redundant 13%, antimonous oxide 3%, glass fibre 25%, compatilizer 8%, oxidation inhibitor 0.5%, oxide compound 0.5%.The each raw material weighing up is put into high mixer, mix 3 minutes, discharging, then uses twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 220～255 DEG C, and forcing machine comprises nine warm areas, wherein one section 220 DEG C, and two sections 250 DEG C, three sections 255 DEG C, four sections 255 DEG C, five sections 255 DEG C, six sections 240 DEG C, seven sections 230 DEG C, eight sections 230 DEG C, nine sections 230 DEG C, screw rod revolution is 40Hz.
the preparation (four) of embodiment 4 PA66 matrix materials
The limiting viscosity of PA66 is 2.8 dl/g, the raw material that compound flame redundant is BPS 50%, magnesium hypophosphite 25% and talcum powder 25% by weight percent content forms, glass fibre is the alkali free glass fibre of surface through silane coupling agent processing, compatilizer is maleic anhydride graft POE, oxidation inhibitor is oxidation inhibitor 1330, and oxide compound is ferric oxide.
Take each feed composition: PA66 68% by following weight percent content, compound flame redundant 6%, antimonous oxide 3%, glass fibre 20%, compatilizer 2%, oxidation inhibitor 0.9%, oxide compound 0.1%.The each raw material weighing up is put into high mixer, mix 4 minutes, discharging, then uses twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 220～255 DEG C, and forcing machine comprises nine warm areas, wherein one section 220 DEG C, and two sections 250 DEG C, three sections 255 DEG C, four sections 255 DEG C, five sections 255 DEG C, six sections 240 DEG C, seven sections 230 DEG C, eight sections 230 DEG C, nine sections 230 DEG C, screw rod revolution is 38Hz.
the preparation (five) of embodiment 5 PA66 matrix materials
The limiting viscosity of PA66 is 3.2 dl/g, the raw material that compound flame redundant is BPS 50%, magnesium hypophosphite 25% and talcum powder 25% by weight percent content forms, glass fibre is the alkali free glass fibre of surface through silane coupling agent processing, compatilizer is maleic anhydride graft POE, oxidation inhibitor is antioxidant 300, and oxide compound is ferric oxide.
Take each feed composition: PA66 45% by following weight percent content, compound flame redundant 10%, antimonous oxide 15%, glass fibre 24%, compatilizer 5%, oxidation inhibitor 0.4%, oxide compound 0.6%.The each raw material weighing up is put into high mixer, mix 5 minutes, discharging, then uses twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 220～255 DEG C, and forcing machine comprises nine warm areas, wherein one section 220 DEG C, and two sections 250 DEG C, three sections 255 DEG C, four sections 255 DEG C, five sections 255 DEG C, six sections 240 DEG C, seven sections 230 DEG C, eight sections 230 DEG C, nine sections 230 DEG C, screw rod revolution is 30Hz.
the preparation (six) of embodiment 6 PA66 matrix materials
The limiting viscosity of PA66 is 2.5 dl/g, the raw material that compound flame redundant is BPS 60%, magnesium hypophosphite 20% and talcum powder 20% by weight percent content forms, compatilizer is maleic anhydride grafted polystyrene, and oxidation inhibitor is oxidation inhibitor 1330, and oxide compound is ferric oxide.
Take each feed composition: PA66 47% by following weight percent content, compound flame redundant 16%, antimonous oxide 10%, glass fibre 22%, compatilizer 4%, oxidation inhibitor 0.7%, oxide compound 0.3%.The each raw material weighing up is put into high mixer, mix 4 minutes, discharging, then uses twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 220～255 DEG C, and forcing machine comprises nine warm areas, wherein one section 220 DEG C, and two sections 250 DEG C, three sections 255 DEG C, four sections 255 DEG C, five sections 255 DEG C, six sections 240 DEG C, seven sections 230 DEG C, eight sections 230 DEG C, nine sections 230 DEG C, screw rod revolution is 40Hz.
the preparation (seven) of embodiment 7 PA66 matrix materials
The limiting viscosity of PA66 is 2.8 dl/g, the raw material that compound flame redundant is BPS 50%, magnesium hypophosphite 25% and talcum powder 25% by weight percent content forms, glass fibre is the alkali free glass fibre of surface through silane coupling agent processing, compatilizer is maleic anhydride graft POE, oxidation inhibitor is oxidation inhibitor 1330, and oxide compound is magnesium oxide.
Take each feed composition: PA66 60% by following weight percent content, compound flame redundant 7%, antimonous oxide 6%, glass fibre 23%, compatilizer 3%, oxidation inhibitor 0.6%, oxide compound 0.4%.The each raw material weighing up is put into high mixer, mix 3 minutes, discharging, then uses twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 220～255 DEG C, and forcing machine comprises nine warm areas, wherein one section 220 DEG C, and two sections 250 DEG C, three sections 255 DEG C, four sections 255 DEG C, five sections 255 DEG C, six sections 240 DEG C, seven sections 230 DEG C, eight sections 230 DEG C, nine sections 230 DEG C, screw rod revolution is 35Hz.
It should be noted that, the glass fiber reinforced PA66 matrix material that embodiment 1-7 is obtained carries out performance test, adopt ASTM standard, test result shows: the PA66 matrix material of preparation has higher GWIT value and CTI value, and flame retardant resistance, tensile strength and the flexural strength of matrix material all meet the requirements.
embodiment 8～9 and comparative example 1～7
The limiting viscosity of PA66 is 2.8 dl/g; The raw material that compound flame redundant is BPS 50%, magnesium hypophosphite 25% and talcum powder 25% by weight percent content forms; Common fire retardant can be triphenylphosphate, TDE, decabromodiphynly oxide, magnesium hydroxide, red phosphorus etc., and the present invention all adopts TDE; Glass fibre is the alkali free glass fibre of surface through silane coupling agent processing; Compatilizer is maleic anhydride graft POE; Oxidation inhibitor is oxidation inhibitor 1330; Oxide compound is ferric oxide.
Take each feed composition by the weight percent content shown in table 1 (%).The each raw material weighing up is put into high mixer, mix 5 minutes, discharging, then uses twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 220～255 DEG C, and forcing machine comprises nine warm areas, wherein one section 220 DEG C, two sections 250 DEG C, three sections 255 DEG C, four sections 255 DEG C, five sections 255 DEG C, six sections 240 DEG C, seven sections 230 DEG C, eight sections 230 DEG C, nine sections 230 DEG C, screw host revolution is 35Hz, and feeding revolution is 13 Hz.
Each composition of raw materials in table 1 embodiment 8～9 and comparative example 1～7
embodiment 10 performance tests
Adopt ASTM standard, the PA66 matrix material that embodiment 8～9, comparative example 1～7 are prepared carries out performance test, and test result is as shown in table 2.
The performance test results of table 2 matrix material
Associative list 1 and table 2, as seen from the table, the present invention adopts BACN compound system, compares with traditional common fire retardant, and novel built fire retardant can effectively improve the GWIT value of material; Adding of alkali free glass fibre can make the GWIT value of matrix material obviously improve, and compatilizer can improve the impact property of material; Ferric oxide has considerable influence to carrying high CTI value.
GWIT value and the CTI value of matrix material of the present invention are higher, flame retardant effect is better, matrix material environmental protection, over-all properties equilibrium, can be widely used in the product of the field of electronics such as Low-voltage Electronic capacitor case, load break switch, carbon brush supports, breaker of plastic casing.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, do not departing under the prerequisite of the inventive method; can also make some improvement and supplement, these improvement and the supplementary protection scope of the present invention that also should be considered as.
Claims (7)
1. high CTI value, a high GWIT value environment-protection flame-proof fiberglass reinforced plastic PA66 material, is characterized in that, described material comprises the feed composition of following weight percent content:
PA66 45%～68%，
Compound flame redundant 6%～20%,
Antimonous oxide 3%～15%,
Glass fibre 20%～30%,
Compatilizer 2%～10%,
Oxidation inhibitor 0.1%～1%,
Oxide compound 0.1%～1%,
Described compound flame redundant is made up of the feed composition of following weight percent content: brominated Polystyrene 50%, magnesium hypophosphite 25%, talcum powder 25%; Described glass fibre is the alkali free glass fibre of surface through silane coupling agent processing; Described oxide compound is ferric oxide.
2. high CTI value according to claim 1, high GWIT value environment-protection flame-proof fiberglass reinforced plastic PA66 material, is characterized in that, described PA66 is polyhexamethylene adipamide, and its limiting viscosity is 2.8 dl/g.
3. high CTI value according to claim 1, high GWIT value environment-protection flame-proof fiberglass reinforced plastic PA66 material, is characterized in that, described compatilizer is maleic anhydride graft POE.
4. high CTI value according to claim 1, high GWIT value environment-protection flame-proof fiberglass reinforced plastic PA66 material, is characterized in that, described oxidation inhibitor is Hinered phenols antioxidant.
5. high CTI value according to claim 4, high GWIT value environment-protection flame-proof fiberglass reinforced plastic PA66 material, is characterized in that, described oxidation inhibitor is oxidation inhibitor 1330.
6. a preparation method for high CTI value, high GWIT value environment-protection flame-proof fiberglass reinforced plastic PA66 material, is characterized in that, comprises the steps:
(1) take each raw material according to weight percent claimed in claim 1;
(2) the various raw materials that weigh up are put into high mixer, mix 2～5 minutes, discharging, then uses twin screw extruder extruding pelletization.
7. preparation method according to claim 6, is characterized in that, the processing temperature of described twin screw extruder is 220～255 DEG C, and screw rod revolution is 30～40Hz.
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| CN103665858A (en) * | 2013-11-18 | 2014-03-26 | 安徽宜万丰电器有限公司 | Perlite powder modified nylon 66 material for automobile plastic part |
| CN104017363A (en) * | 2014-06-06 | 2014-09-03 | 宁波伊德尔新材料有限公司 | High-temperature-resistance flame-retardant glass fiber reinforced PA46/PA66 composite material and preparation method thereof |
| CN104072981A (en) * | 2014-07-14 | 2014-10-01 | 苏州创佳塑胶有限公司 | Halogen-free flame retardant polyamide material and preparation method thereof |
| CN104974516B (en) * | 2015-06-25 | 2018-09-28 | 东莞市众一新材料科技有限公司 | A kind of High glow wire halogen-free flame retardant composite material and preparation method |
| DE102016203221A1 (en) * | 2016-02-29 | 2017-08-31 | Clariant Plastics & Coatings Ltd | Flame retardant polyamide composition |
| CN108047705B (en) * | 2017-12-12 | 2020-12-04 | 天津金发新材料有限公司 | Flame-retardant polyamide composition and preparation method thereof |
| CN109401303B (en) * | 2018-10-31 | 2021-09-03 | 中山市华邦塑料有限公司 | Reinforced flame-retardant nylon composition with high glowing filament ignition temperature and preparation method thereof |
| CN109735100B (en) * | 2018-12-28 | 2021-08-20 | 金发科技股份有限公司 | Antimonide-free halogen-containing flame-retardant polyamide composite material and preparation method thereof |
| CN113388248B (en) * | 2021-07-21 | 2022-09-16 | 合诚技术股份有限公司 | high-CTI brominated flame-retardant reinforced polyamide composite material and preparation method and application thereof |
| CN114085522B (en) * | 2021-12-31 | 2024-03-08 | 焦作同辐科技有限责任公司 | High CTI (comparative tracking index) halogen-free flame-retardant glass fiber reinforced PA66/PPO (polyamide-66/Poly-phenylene oxide) composite material and preparation method thereof |
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| US8440756B2 (en) * | 2009-09-14 | 2013-05-14 | Mitsubishi Gas Chemical Company, Inc. | Flame-retardant polyamide resin composition |
| CN102040827B (en) * | 2009-10-22 | 2012-08-22 | 上海日之升新技术发展有限公司 | Environmentally-friendly flame-retardant reinforced PA66 composite material of high glowing filament and preparation method thereof |
| CN102108187B (en) * | 2009-12-28 | 2012-09-12 | 上海日之升新技术发展有限公司 | High glowing filament environmental-friendly inflaming retarding reinforced polybutylece terephthalate (PBT)/acrylonitrile butadiene styrene (ABS) alloy material and preparation method thereof |
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